Glycol esters of acyloxycarboxylic acids



Patented Dec. 18, 1951 GLYCOL ESTERS OF ACYLOXYCARBOXYLIC ACID Edward M. Filachione, Philadelphia, Pa., Martin L. Fein, Riverside, N. J and Charles H. Fisher, Abington, Pa., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application June 18, 1948, Serial No. 33,837-

8 Claims. (01. 260- -4 84) (Granted under the act of March 3, 1883, as.

amended April 30, 1928; 370 O. G. 757) This application is made under the act of March 3, 1883, as amended by the act of April 30, l928,and the invention herein described, if patented in any country, may be manufactured and used by or for the Government of the United States of America for governmental purposes throughout the world Without the payment to us of any royalty thereon.

This application is a continuation-in-part of our copending application for patent, Serial No. 770,179, filed August 22, 1947, now Patent No. 2,534,255, the disclosure of which is incorporated herein by reference.

This invention relates to glycol esters of acyloxycarboxylic acids and has among its objects the provision of such esters and processes for their preparation. Other objects and advantages will be apparent from the description of the invention.

We have found that glycol esters of acyloxycarboxylic acids, which possess valuable proper ties as solvents, plasticizers and modifying agents for plastic compositions, can be obtained by reacting a glycol, or a glycol ester containing at least one unsubstituted hydroxyl group, with an ester of a hydroxycarboxylic acid and treating the resulting glycol ester thus formed by alcoholysis, with an acylating agent According to the invention the glycol, or glycol ester containing at least one unsubstituted hydroxyl group, is subjected to alcoholysis by heating at reaction temperature with an alkyl ester of a hydroxycarboxylic acid, preferably in the presence of a reaction catalyst and with concurrent removal from the reaction mixture, of the alkanol formed in the alcoholysis process. The glycol ester thus obtained is then acylated by interaction with an organic acylating agent to form glycol esters corresponding to the general formula I R-ORO- wherein R is an alkylene radical containing from 2 to 6 carbon atoms, and R and R are acyl radicals of saturated aliphatic monocarboxyllc acids at least one of said acyl radicals being derived from an alpha-acyloxycarboxylic acid.

The process of this invention is applicable to glycols in general; that is, to aliphatic dihydric alcohols, such as ethylene glycol, propanediol 1,2 and 1,3, butanediol 1,3; 2,3; and 1,4; pentanediol 1,2; 1,4 and 1,5; hexanediol 1,6; 2-ethylhexanediol 1,3, and the like, and to the esters of aliphatic dihydric alcohols which contain at least one free hydroxyl group. Suitable esters include, for example, the monoesters of the above-listed glycols with saturated aliphatic monocarboxylic acids containing from '5 to 18 carbon atoms, like caproic, caprylic, lauric, palmitic or stearic acid; hydroxycarboxylic acids like glycolic or lactic acid; and diesters of saturated aliphatic dicarboxylic acids like succinic, adipic, sebacic, azelaic, diglycolic, and the like.

Esters of hydroxycarboxylic acids adapted for use in the alcoholysis process are the lower alkyl esters such as methyl, ethyl and propyl esters of the lower, saturated, aliphatic, alpha-hydroxymonocarboxylic acids like glycolic and lactic acid or alpha-hydroxyisobutyric acid.

Suitable alcoholysis catalysts include acidic substances such as sulfuric or toluene sulfonic acids, as Well as other esterification catalysts, like metal alcoholates, as for instance, aluminum ethoxide and aluminum isopropoxide.

The products of the alcoholysis reaction can be acylated in a conventional manner by treatment with an organic acylating agent. Suitable I acylating agents include ketene and the anhydrides or halides of carboxylic acids, as for example, acetic anhydride, propionic anhydride, acetoxypropionyl chloride, pelargonyl chloride, and so forth.

Since in the alcoholysis process the alkyl esters of hydroxycarboxylic acids are capable ofv reacting not only with the alcohol groups of the glycol radicals but also with the other hydroxyl groups of the reactants and reaction products the process usually yields products comprising a number of components. The composition of the product obtained and the molecular weight of the predominant constituents can be controlled within certain limits by varying the proportions of the reactants, the duration of the alcoholysis process and the amount of alkylol removed from the reaction mixture.

The following Examples I to III, inclusive, illustrate the preparation of glycol esters of the present invention. I

EXAMPLE I Preparation of ethylene glycol monolactate diacetoazypropionate A mixture of 869g. (14 moles) ethylene glycol, 728 g. ('7 moles) methyl lactate and '7 g. aluminum isopropoxide, was heated at atmospheric pressure in' a flask fitted with a-2-foot Vigreauxtype distilling column. Approximately 282 cc. methanol distilled from the reaction mixture. Low-boiling components were then removed by heating the contents ofthe flask at about of the acylating agent the temperatum ofthe.

reaction mixture was maintained-below=- 20 'C; by cooling the flask with ice water." When-the acylation was completed, waterwas added to dissolve the pyridine hydrochloride precipitate.

The oil layer thus obtained was separated;

washed several times with concentrated acne-.- ous solution of sodium chloride, dried. over anhydrous sodium sulfate and distilled to 'remove the benzene.

boiling at 175-180 C./0.4;mm., which consisted essentially of ethylene glycol monolactate. diacetoxypropionate having the: following, .charac teristics: n ?=1.4416; d4 =1.l963; and ester equivalent- 73.1.

EXAMPLE-II Preparation of the LS-pentanedibl dilactate d2- propionate and vdi- Z-ethylhezroate) A mixture of technical grade. .ljrpentanediol (2-moles, 208' g.) ,.methyl lactate .(6; moles,,.62.4: and 3, grams of p-toluenesulfonicacid- (mono.- hydrate) catalyst was heated ,at..atmospheric pressurein afiask fittedwith .a,2-I"oot;Vigr.eaux type distilling column. 162 ml-. methanol was distilled from the reaction. mixture. over. a. pcriodof abo.ut.5 hours while; the temperaturein the flask. rose from. 107 .C. to 152? C. After allowingttheflaskpto cool,.the excess methyl .lac-

tate was distilled under reduced pressure- The distillation residue,v consisting essentially of 1,5- pentanediol s.dilactate,.was divided; into ,two. equal portions, each approximately,equivalent-to onehalf mole.

One portion wasztreated withan equivalent amount of propionic anhydride -to-acylate-.the

free hydroxylgroups. Propionic acid; was distilled at reduced pressure, and residual free acidity was, washed out-of an ethernsolut-ion" of the product with water and. NaI-ICOrsolution. The finalproduct, 1,5-pentanediol vdilactatedipropionate, when dry andifree of ether, had an index-cf refraction (N of 1.4402.

The other portion of,1,5-pentanedioh-dilactate was treated with a. slight excess :of, 2-ethylheXQyl chloride using the followingprocedure:

The chloride was added in-asmall quantities to a cooled, stirred solution of the dilactate inv200 ml. of ether and drypyridine (weight-equivalent to that of 2-ethylhexoyl chloride). When-reaction seemed to be complete, 100-ml.--water was added to dissolve the pyridine hydrochloride formed in the reaction; The oil, layer :was separated and washed with dilute HCl solution-.sevoral times, then with wateranid NaHCO3-NaCl solution until acid ,free. The, final product, 1,5- pentanediol dilactate di-(Z-ethylhexoate), when dry and ether free, had an index of refraction (N 3 of 1.4458.

III

Preparation of the r1.-; -pentanediol .dz'lactyllac The residual -material was. then. distilled in vacuum yielding a middle fraction.

Lil

4 moles) methyl lactate in the presence of 2 g. toluene. sulfonic acid. The product .thus obtained, consisting/essentially of 1,5-pentanediol lactyllactate, was divided into two equal portions which were treated with acetic anhydride and propionic anhydride respectively, using a small'amount'of concentrated sulfuric acid as catalyst. The acylation products recovered from themeactionmixtures by methods analogous to those describedinthe foregoing examples were washed acid free and had the following characteristics:

1,5-pentanediol polyactate propionate, N 1.4410,, ester eq.,=87; d4 =1.12'75; 1,5-pentanediolzrpolylactate acetate, N =1.4410, ester eq.=

EXAMPLE IV Preparationof ethylene glycol adipate lactate propz'onate Ethylene glycol adipate was prepared by reacting 292 g. (2 moles) adipicacidwith 248g. (4 moles) ethylene glycol, using 1.ml. concentrated H2304 as catalyst and 300 m1. benzeneas entraining agent. When the esterification reaction was complete (approximately 4 hours), the entraining agent was removed by distillation.

One mole ethylene glycol adipate (one-half the material described above) was :reacted with 5 moles methyl lactate with 1 gram petoluene sulfonic acid (monohydrate) as catalyst. This ester interchange yielded approximately 2.1n0les methanol in about 4 hours. The .excess methyl lactate was distilled under reduced pressureand the residue, consisting essentially of ethylene glycol adipate lactate, was then treated with propionic anhydride, using about 1.05 equivalents of anhydride to acylate all hydroxylgroups. After distillation of propionic, acid formed. in, acylation, the product was dissolved in ether andwashed acid-free with NaCl and NaHCOa solutions. The ether layer was then dried and'the ether distilled. The final product, essentially ethylene glycol adipate lactate propionate, had the following in- In the foregoing examples methyl lactate can be replaced by anequivalent amount of .another lower alkyl ester of lactic acid, such-as ethyLor propyl lactate, and-other esterification, catalysts,

r for example sulfuric: acid or aluminumepoxide,

maybe used in the alcoholysis reaction. Analogous results are also, obtained usin v esters .of

other lower alpha-hydroxy carboxylic acids.1ikeglycolic acid, and otheracylatingagents The following examples illustrate the useiof the compounds of-th-is invention-with synthetic plastics such as organic cellulose esters, cellulose ethers, and-polyvinyl compounds in the production of plastic compositions.

EXAMPLE V 4.8 g. of. cellulose acetate and 1.2 g; of 'the ethylene glycol -monolactate diacetoxypropionate of Example I were, dissolved: in acetone. Theresulting clear solution was poured into a Petri dish and covered with a'watch glass to allow'slow evaporation .of the solvent. The clean dry; tough and: flexible film thus F obtained remained essentially unchanged onheatin at 65 C. fon several hours;

EXAMPLE VI Following the procedure described in the foregoing example and using cellulose acetate butyrate instead of cellulose acetate a film having characteristics similar to that of the film of Example V was obtained.

EXAMPLE VII 4.8 g. of ethyl cellulose and 1.2 g. of the 1,5- pentanediol polylactate acetate of Example 111 were dissolved in a solvent mixture consisting of 40 ml. toluene and ml. ethanol. The clear solution was allowed to evaporate slowly in a covered Petri dish. A clear, dry, tough flexible film was formed. A similar film was obtained using 1,5-pentanecliol polylactate propionate as the plasticizing agent.

EXAMPLE VIII Clear, dry, tough and flexible films were obtained by the procedure described in Example V using 1,5-pentanediol polylactate acetate or propionate instead of ethylene glycol monolactate diacetoXyprop-ionate as the plasticizing agent.

EXAMPLE IX 35 parts of a copolymer of 95 parts vinyl chloride and 5 parts vinyl acetate were combined with parts of 1,5-pentanediol polylactate propionate on the compounding mill, and the resulting sheet molded at 300 F. and 12T total pressure for 2 minutes. The product showed satisfactory compatibility following conditioning for 64 hours at 77 F. and 50% R. H.

Having thus described our invention we claim:

1. A process comprising subjecting a compound selected from the group consisting of a glycol containing from 2 to 6 carbon atoms and a saturated ester of said glycol containing at least one free hydroxyl group to alcoholysis by heating it at reaction temperature and in the presence of an esterification catalyst, with a. lower alkyl ester of a lower aliphatic alpha-hydroxymonocarboxylic acid, with concurrent removal of the alcohol formed from the reaction mixture, and then reacting the resulting glycol ester with an acylating agent.

2. A process comprising subjecting ethylene glycol to alcoholysis by heating it at reaction temperature and in the presence of an esterification catalyst, with methyl lactate, with concurrent removal of the methanol formed from the reaction mixture, and then reacting the resulting glycol ester, which consists essentially of ethylene glycol monolactate, with alpha-acetoxy-propionyl chloride as an acylating agent to produce ethylene glycol monolactate diacetoxypropionate.

3. A process comprising subjecting 1,5-pentanediol to alcoholysis by heating it at reaction temperature and in the presence of an esterification catalyst, with methyl lactate, with concurrent removal of the methanol formed from the reaction mixture, and then reacting the resulting glycol ester, which consists essentially of 1,5- pentanediol lactyllactate, with propionic anhydride as an acylating agent to produce 1,5-pentanediol dilactyllactate dipropionate.

4. A process comprising subjecting ethylene glycol adipate to alcoholysis by heating it at reaction temperature and in the presence of an esterification catalyst, with methyl lactate, with concurrent removal of the methanol formed from the reaction mixture, and then reacting the resulting glycol ester, which consists essentially of ethylene glycol adipate lactate, with propionic anhydride as an acylating agent to produce ethylene glycol adipate lactate propionate.

5. A compound selected from the group consisting of ethylene glycol monolactate diacetoxyprop-ionate, 1,5-pentanediol dilactyllactate dipropionate, and ethylene glycol adipate lactate propionate.

6. Ethylene glycol monolactate diacetoxypropionate having the formula 7. 1,5-pentanediol dilactyllactate dipropionate having the formula 8. Ethylene glycol adipate lactate propionate having the formula EDWARD M. FILACHIONE. MARTIN L. FEIN. CHARLES H. FISHER.

REFERENCES CITED The following references are of record in th file of this patent:

UNITED STATES PATENTS .Number Name Date 2,072,102 Dreyfus Mar. 2, 1937 2,106,703 Cox et al Feb. 1, 1938 2,137,007 Schrauth et a1 Nov. 15, 1938 2,151,185 Carruthers Mar. 21, 1939 2,158,107 Carruthers May 16, 1939 2,196,758 Dickey Apr. 9, 1940 2,207,702 Straughn July 16, 1940 2,290,128 Loder July 14, 1942 2,350,388 Claborn -1- June 6, 1944 2,359,750 Collins Oct. 10, 1944 2,388,164 Loder Oct. 30-, 1945 FOREIGN PATENTS Number Country Date 445,223 Great Britain Apr. 6, 1936 Great Britain May 8, 1939 

1. A PROCESS COMPRISING SUBJECTING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A GLYCOL CONTAINING FROM 2 TO 6 CARBON ATOMS AND A SATURATED ESTER OF SAID GLYCOL CONTAINING AT LEAST ONE FREE HYDROXYL GROUP TO ALCOHYLSIS BY HEATING IT AT REACTION TEMPERATURE AND IN THE PRESENCE OF AN ESTERFICATION CATALYST, WITH A LOWER ALKYL ESTER OF A LOWER ALIPHATIC ALPHA-HYDROXYMONOCARBOXYLIC ACID, WITH CONCURRENT REMOVAL OF THE ALCOHOL FORMED FROM THE REACTION MIXTURE, AND THEN REACTING THE RESULTING GLYCOL ESTER WITH AN ACYLATING AGENT. 